Horace s



@atented @ct. l6, 1%53 PRODUCTION OF HALOHYDRIN ETHERS OF PHENOLS UnisL. Davis and Horace S. Knight, Berkeley, and John R. Skinner, SanFrancisco, Calif., assignors to Shell Development Company, San

Francisco, Calif., a corporation oi Delaware No Drawing. Application May27, 1949, Serial No. 95,878

8 Claims. (Cl. 260-613) that provid a surprising and greatly improvedreaction.

The production of ethers from the reactants employed in the presentprocess necessarily in-- volves a reaction between epoxide and hydroxylgroups such as,

Various procedures are known in the art to cause such a reaction tooccur. The reaction can be accomplished in the absence of catalysts; U.S. Patents 1,635,927 and 1,730,061 describe the condensation ofhydrocarbon epoxides with phenols at high temperatures and pressures.The uncatalyzed reaction, however, is slow, and a catalyst is requiredto obtain a practical reaction rate. Both acidic and basic catalysts areknown to provide a suitable rate of reaction. When the epoxide compoundcontains halogen atoms, the ethers contain halohydrin radicals.Halohydrin radicals readily lose a molecule of a hydrogen halide to formepoxide radicals when they are contacted with many basic-reactingcompounds (as in the production of epichlorohydrin from the glyceroldihalohydrins). The alkali metal hydroxide catalyzed reaction betweencompounds containing halogen atoms and epoxide groups is a known methodof producing glycidyl ethers which are substantially free of halogen,see for example U. S. Patents 2,221,818 and 2,324,483.

Where a halohydrin ether is desired it has heretofore been necessary toemploy acidic catalysts such as acidic inorganic fluorine compounds andmetal halides, see for example U. 8. Patents 2,260,753, 2,327,053 and2,428,235. However, when a phenol is so condensed by the action of anacidreacting catalyst, the yield of halohydrin ether is materiallyreduced by a different type of further reaction. The acid causes arearrangement of the halohydrin ether in which the oxy group of theether becomes the hydroxyl group of a substituted phenol.

The present invention provides a process for producing halohydrin ethersof phenols which substantially completely avoids the dised nt-eginherent in the production of such ethers from phenols and compoundscontaining halogen atoms and epoxide groups by the methods heretoforeknown. Substantially no monomeric or polymeric glycidyl ethers areformed and substantially no rearrangement of the halohydrin ethers tosubstituted phenols occurs when halohydrin ethers are produced inaccordanc with the present invention.

The improved process provided by the invention is made possible by thediscovery that one particular class of basic catalysts surprisinglyexhibits the properties of both acidic and basic types of catalysts.They resemble the acidic catalysts in that they do not catalyze theconversion of halohydrin ethers to epoxide-containing ethers. 'I'heyresemble the general class of basic catalysts in that they do notcatalyze the rearrangement of halohydrin ethers to substituted phenols.we have found that these properties are unique in the hydroxides andorganic oxides of calcium. They are exhibited by calcium hydroxide, aswell as by the calcium salts of organic oxy-compounds, i. e.. by thecalcium phenolates or alcoholates. The term organic oxides of calciumis: used herein to refer to the calcium salts of the organicoxy-compounds, i. e., of phenols and of alcohols. See Example IV below,under the same conditions alkali metal hydroxides, which are oftenequivalent to calcium hydroxide, catalyze the reformation of epoxidegroups. Even the more closely related alkaline earth metal hydroxides,magnesium hydroxide and barium hydroxide react I amounts of polyarylethers of polyhydric alcohols.

The former, by the action of a base, can be reconverted to the startingmaterials, and the latter I provides a valuable by-product of theprocess.

The hydroxides and organic oxides of calcium catalyze the condensationbetween hydroxyl comconditions of temperature, pressure, concentrationof reactants and proportions of reactants heretofore used for suchreactions.

In general, any temperature from about C. to the decompositiontemperature of the reactants can suitably be employed. The range of fromabout 50 C. to about 100 C. is particularly suitable.

Any pressure above the vapor pressure of the reactants can suitably beemployed, and in general, atmospheric pressure is particularly suitable.

The reactants can be diluted with up to about volumes of an organicsolvent such as a normally liquid ke tone, ether or hydrocarbon. Thealiphatic ketones, such as methyl isobutyl ketone, are particularlysuitable. The reactants can be employed in equivalent amounts or eithermay be employed in an excess of up to about 10 to 1. The employment of amolar excess of from about 2 to 4 equivalents of the epoxide reactant isparticularly suitable.

The present invention provides a new class of catalysts for the generalreaction. the condensation of hydroxy-compounds with epoxy compounds. Ithas been demonstrated (see Examples I to IV below), that whenever theepoxy compound contains halogen atoms and the hydroxy compound is aphenol, the process of the invention provides the surprising andvaluable result mentioned above. The invention is therefore applicableto the employment of any of the epoxide compounds which have heretoforeexhibited the property of condensing with a hydroxy compound. Ingeneral, any halogen-containing organic compound containing an epoxidering of not more than four atoms condenses with a phenol to formhalohydrln ethers when the reaction is conducted in accordance with thepresent invention. Substituted aliphatic hydrocarbons containing avicinal epoxide group (an epoxy oxygen atom attached to adacent carbonatoms) and at least one halogen atom are preferred reactants, andvicinal epoxy-substituted alkyl chlorides (eplchlorolwdrin and itshomoiogs) are particularly preferred.

Illustrative examples of epoxide compounds which condense with phenolsin the improved manner when the reaction is conducted in accordance withthe process of the invention include epichlorohydrin, epibromohydrin,s-methylepichlorohydrin, ,-diethylbromohydrin, heptyleplchlorohydrin,epiiodohydrin, epifluorohydrin, chloromethylglycidyl ether, glycidylchloroacetate, a-cyclohexylepichlorohydrin, p-phen- 5 ylepibromohydrin,glycidyl chlorobenzoate and a-allyleplchlorohydrin.

In general, any phenol is a suitable reactant for use in the presentprocess. The term phenol" as employed in a generic sense refers to anaromatic hydroxy compound in which hydroxyl groups are directly linkedto the aromatic nucleus. Phenols containing a single hydroxyl group or aplurality of hydroxyl groups attached to non-adjacent carbon atoms arepreferred, and

those which are aromatic hydrocarbons contain- 4 droxydiphenyl,l,4-dihydroxynaphthalene, 9,10- dihydroxyanthracene and1,3,6-trihydroxynaphthalene.

The hydroxides and the organic oxides of calcium, i. e.. compounds ofthe formula C8.(OR)2 where It represents hydrogen or an organic radicala carbon atom of which is attached to the oxygen atom of the formula,comprise the catalysts contemplated for employment in the proces of thepresent invention. Calcium hydroxide and the hydrocarbon oxides ofcalcium (compounds of the above formula where each R represents ahydrocarbon radical) are preferred, and calcium hydroxide and the aryloxides of calcium are particularly preferred. Illustrative examples ofcompounds which can suitably be employed as catalysts in the process ofthe present invention include calcium hydroxide, calcium phenolate,calcium ethylate, calcium actylate. calcium hydroxy butylate, calciumbenzylate, the calcium cresolates and the calcium xylolates.

It is preferred to employ the catalyst in less than the amount requiredto furnish an equivalent of base for each hydroxyl group of the phenol.The range of from 10 to 50 per cent of the equivalent amount ispreferred, but amounts substantially in excess of the equivalent amountcan suitably be employed.

It is preferred to conduct the process of the invention in a reactionmedium containing an appreciable amount of water, from about 1 to 10moles per mole of the calcium compound being generally suitable. Anamount of between about 4 and 9 moles per mole of calcium compound hasbeen found to be particularly suitable.

The hydroxides and organic oxides of calcium can suitably be formed insitu; for example, by a reaction between water and/or the phenol andcalcium oxide or metallic calcium in a reaction medium containing theepoxide and phenolic reactants and an appreciable amount of water.

The following examples are presented for the purpose of illustrating indetail the production of various halohydrln ethers of phenols by theprocess of the invention, and to illustrate the improved resultsinherent in the use of the catalysts described herein. However, as manyvariations in reactants and reaction conditions are within its scope,the invention is not to be construed as limited to the materials orconditions recited in the examples.

Example I Y action mixture). The reaction products can be isolated byfiltering oil the solids and fractionally distilling the filtrate.

That the present process is productive of high yields of halohydrlnethers is demonstrated by the fact that when the above reactants were-heated for only two hours at 0.; 73% of the phenol was converted toethers, 72% being the halohydrln ether and 28% being diphenyl glycerolether. A conversion of 15% of the epichlorohydrin to glyceroldichlorohydrin (which by the action of base can be reconverted toepichlorohydrin) constituted the only other product 76 formed from theepichlorohydrin.

rkh

That the unproven reationis obtained by theuse oi the basic compounds ofcalcium over a wide range of temperatures is demonstrated by the riiy amixture of the mono and bis-monohalohydrin ethers of2,2-bis(4-hydroxyphenyl)- propane with a lesser amount of the glycerolfact that when the same reactants were heated for h two hours at 50 C.,with the exception that a por- 5 Example IV tion oi the phenol wasconverted to calcium pheno- A comparison of various bask; catalysts inthe late, the same derivatives of phenol were proreaction betweenepichlorohydrln and 2.2-bls(4- d ed, hydroxyphenybpropane in a 6 to 1molar ratio:

I Per cent Epoxlde Temp. Time Per cent c uir al "as... he a ass/1a.

1 OagOfigH-DILO 25 to 2.3 13.5 2 Be on i+enio as so as 1.3 0.00s 3 do 2590 1.5 as 0.095 4 105 to 4 0.16 o 418 5 no e0 6 12 s 0. 012 6 25 50 6new vi Ii mcflou 7 25 60-76 3 neg-.igible reaction 8 100 100 4neg.-igiblo reaction "Based on two equivalents of alkali per mole of2,2-bis(4-hydroxyphenyl) propane. Mnhydrous reaction system.

Example 11 The glycerol monochlorohydrin ether of phenol(3-chloro-2-hydroxypropyloxybenzene) is produced in accordance with theprocess of the present invention by heating a mixture of 18 moles ofepichlorohydrln, 6 moles of phenol, 7 moles of water and 0.87 mole ofcalcium phenolate to a temperature at which reaction occurs (asindicated by the development of heat within the reaction mixture). Thereaction products can be isolated by filtering ofi the solids andiractionally distilling the filtrate.

That the present process is productive of high yields of halohydrinethers is demonstrated by the fact that when the above reactants wereheated for only two hours at 90 C., 79% 01 the phenol was converted toethers; 76% being the halohydrin ether and 24% being diphenyl glycerolether. A conversion of 14% or the epichlorohydrln to glyceroldichlorohydrin (which by the action of base can be reconverted toepichlorohydrln) constituted the only other product formed from theepichlorohydrln.

Example III e glycerol monohalohydrin ethers of 23- bis(4-hydroxyphenyl)propane are produced in ac- 01 with the process oi the invention byheating a mixture of 3 moles of 2,2bis(4-hydroxyphenyl) propane, 18moles of epichlorohydrln, 0.87 mole of calcium hydroxide and 8 moles ofwater to a temperature at which reaction occurs. A mixture of the ethersof the phenol can be isolated by filtering the reaction mixture andfractionally distilling ofi the unconverted reactants and volatilecomponents of the filtrate.

That the process of the invention is adapted to the production ofhalohydrin ethers oi polyhydric phenols was demonstrated by isolatingfrom the reaction products obtained by heating the above reactants forseven hours at 90 C., a mixture of phenyl ethers having an epoxide valueof less than 0.01 and containing 13.5% chlorine. A yield of glyceroldichlorohydrin amounting to about a 20% conversion of theepichlorohydrln was also isolated from the liquid reaction products. Asthe mono and bis-monochlorohydrin ethers of2,2-bis(4-hyclroxyphenyl)propane contain 11.0% and 17.2% chlorine,respectively, and as a reaction of the mixture obtained from the abovereaction with sodium hydroxide results in a marked increase in theepoxide value: the mixture That the improved catalysis of the formationof the halohydrin ethers of phenols is a unique property of thehydroxides and organic oxides of calcium is indicated by the fact thatunder the same conditions the use of sodium hydroxide caused thereformation of epoxide groups (or a metathetlcal reaction between theepichlorohydrln and a sodium salt of the phenol), barium hydroxidecaused the hydrolysis of most of the chlorine groups, magnesiumhydroxide, calcium oxide and sodium carbonate caused substantially noreaction, but the use of calcium hydroxide caused an etherificationreaction similar to those described in greater detail in the precedingexamples. 1

We claim as our invention:

1. A process for the production of phenyl about C., the improvementwhich comprisw conducting the reaction in the presence of cai ciumhydroxide.

4. A process for the production of 'glycerol monochlorohydrin ethers ofphenols which comprises reacting epichlorohydrin and a phenol in thepresence of a compound of calcium selected ,from the class consisting oicalcium hydroxide,

calcium phenolates and calcium alcoholates.

5. The process of claim 4 in which calcium hydroxide is employed as thecatalyst.

6. The process of claim 4 in which calcium phenolate is employed as thecatalyst.

7. A process for the production of halohydrin ethers of phenols whichcomprises reacting a phenol with a halo-substituted epoxide compound,wherein the halogen and epoxide groups are the only functional groups,in the presence of a calcium phenolate.

8. A process for the production of halohydrin other; at phenols whichcomprises reacting a phenol with a hole-substituted epoxide com-REFERENCES CITED v wherem the halogen epmdde p The following referencesare of record in the are the only functional groups, in the presence me0! this patent;

of a. compound of calcium selected from the class consisting of calciumhydroxide, calcium pheno- 5 UNITED STATES PATENTS late; and calciumalcoholabes. Number Name Dot;

ORB-IS L. DAVI S. 7 1,971,662 7 Schmidt Aug. 28. 1934 HORACE S. KNIGHT.2,428,235 Marple Sept. 30, 1947 JOHN R. SKINNER.

1. A PROCESS FOR THE PRODUCTION OF PHENYL GLYCEROL MONOCHLOROHYDRINETHER WHICH COMPRISES REACTING PHENOL AND EPICHLOROHYDRIN AT ATEMPERATURE OF FROM ABOUT 50* C. TO ABOUT 100* C. IN THE PRESENCE OFCALCIUM HYDROXIDE.